Motor fuel



Patented Nov. 28, 1939 MOTOR FUEL Ernest M. Marks, Lansdowne, Pa.,

The Atlantic Refining Company, Philadelphia, Pa., a corporation of Pennsylvania No Drawing.

4 Claims.

tics of hydrocarbon motor fuels by the addition .0 thereto of oxidation products of tri-isobutylene.

A further object of this invention is the improvement of the anti-detonation value of motor gasoline by the addition thereto of oxidation products of tri-isobutylene of such boiling range or volatility as not to alter the boiling range of the gasoline to an undesirable extent.

It has been found that tri-isobutylene, per se, is capable of improving the anti-detonation value of motor fuels when added thereto in appreciable quantities, for example, of the order of to 50% by volume. However, since tri-isobutylene is relatively high boiling (355 F.), the addition of substantial quantities thereof to motor fuels within the gasoline boiling range (90 F. to 390 F.) alters the boiling range or volatility of the fuel to an undesirable extent. In other words, the addition of tri-isobutylene to a marketable gasoline having a specified boiling range increases the percentage of the higher boiling components in such fuel to such an extent that the volatility thereof is markedly impaired.

I have discovered that tri-isobutylene may be converted into products more suitable as motor fuel or as addition agents to improve the antidetonation qualities of motor fuels such as gasoline, by a relatively inexpensive and readily operable process involving oxidation. The products formed by the oxidation of tri-isobutylene not only possess good anti-detonation values but are of such boiling range or volatility as to be compatible with gasolines having definite specifications with respect thereto.

In accordance with my invention, tri-isobutylene is subjected to the actionof an oxidizing medium such as air, oxygen or gaseous mixtures containing oxygen. The oxidizing operation may be carried on at substantially atmospheric pressure and at temperatures within "the range of from about 300 F. to about 400 F., preferably in the presence of a catalyst such as the oxides of Mn, Cu, Fe, Cr and V, or the metals Cu, Fe, Cr and V, or the metal salts of organic acids such as copper or manganese oleates or naphthenates. While the oxidation Application November 12, 1936, Serial No. 110,474

may be carried on in the absence of a catalyst,

PATENT OFFICE assignor to particularly at elevated pressures, it is desirable to. employ a catalyst to increase .the rate of the oxidation reaction. When the oxidizing operation is carried on at superatmospheric pres sures, for example, pressures up to about 2000 IS -1bs./sq. in., the temperatures required may be considerably lower than those employed at, at-,; mospheric pressure. Temperatures of the order of 200 F. to 300 F. are suitable when oxidation is effected at pressures of the order of 200 to 10 "1000 lbs/sq. in., in the presence of one or more of the catalysts above mentioned. The choice of temperatures, pressures and time of contact to be employed in effecting oxidation is dependent upon the degree of oxidation and character of the products desired. The oxidizing operation may be carried on ma batch system, or a continuous system, wherein the oxidation products may be separated. from the unconverted hydrocarbons and the latter recirculated for further treatment.

My invention-may be further illustratedby the following example, but is in no wise limited thereto. 1

1 bbl. of tri-isobutylene (boiling range 340 F.-355, F.) together with 2.5% by weight of finely divided MnOz was charged to a suitable vessel provided with a vapor outlet and condenser. The mixture was continuously agitated and gradually heated, oxygen being bubbled through the liquid at a rate of about 4 cubic feet. per minute. Oxidation reactions started at a temperature of about 260 F. with the formation of water, lower-boiling oily products and gas. These products were continuously distilled off as they were formed, separation from the reaction mixture being thus obtained. As the oxidation progressed, the temperature was increased to a maximum of 370 F., and the oxidation continued until no further oily distillate and water were obtained. The oily distillate was separated from the water, which latter was neutralized with sodium hydroxide and then treated with soda ash to effect a salting out of additional oily material. The initial oily distillate, after neutralization, was admixed with the oily material recovered from the aqueous distillate by the salting-out procedure, and the mixture was fractionally distilled to separate any unconverted tri-isobutylene. The oxidized, oily product thus obtained had a specific gravity of 0.82 at 60 F., a distillation range of from 144 F. to 327 F., an average molecular weight of 84, and contained 66.1% C, 13.1% H, and 20.8% 0.

In order to determine the effectiveness of the tri-isobiitylne oxidation product as an antidetonation agent for motor fuel, 25% by volume tially to increase its anti-detonation characterof the product as above described was blended istics, said oxidation product boiling within the with a straight-run gasoline and tested for antiboiling range of gasoline and resulting from thedetonation value or octane number in accordance oxidation of tri-isobutylene .under conditions with the A. S. T. M.C. F. R. Method D357-34T. such that the ratio of oxygen to tri-isobutylene 5 is at least mol for mol.

Motormel o t 2. The method of increasing the anti-detona- "m tion characteristics of gasoline, whic comprises P 1 m t r adding to the gasoline an oxidation product of 10 tri-isobutylene is an'amount sufficient substantiiittt firfifffiti fi'f.iiiiti ffl?.flfiiffi'fi'fi 54 tially to increase its anti-detonation characteristlcs, said oxidation product boiling within the It will be seen from the above example that boiling range gasoline nd resulting from the the oxidation products of tri-isobutylene, when Oxidation tri-isobuwlene at temperatures of 1 blended with a hydrocarbon motor fuel, improves from about to about and under 5 the anti-detonation value thereof to a marked conditims Such that ratio 0f oxygen to degree. The oxidation products may be emisobutylene is at least 11101 for m played, per Se, a motor fuel or may e added 3. A motor fuel of improved anti-detonation to gasoline in any d i d proportion. f r characteristics, comprising gasoline to which has 20 ample, 10%, 2 5%, 50% r more, depending upon been added an oily liquid oxidation product of the degree of improvement required. The blend- ,tliisobutylene boiling Within the a o n b011- ing of tri-isobutylene oxidation products is not 8 range and resulting o he Oxidat on of necessarily confined to hydrocarbon motor fuels, tri-isobutylene under hditi0ns in which e since such oxidation products may be added to rat-10 f oxygen to yl ne s at least mol 25 mixtures of gasoline and alcohol, gasoline and benzol, and the like. Other motor fuels, such motor u of improved anti-detonation as cracked gasoline and gasoline produced by characteristics, comprising s ne o Wh ch has the chemical or thermal polymerization of gasebeen added an y liquid Oxidation P o u t Of oils hydrocarbons, as well as straight run gastri-isobutylene boiling Within the gasoline boil- 0 oline, may be improved by the additi of tning range and resulting from the oxidation of 3 isobutylene oxidation products. tri-isobutylene at temperatures of from about What I claim is: 200 F. to about 400 F. and under conditions in 1.- The method of increasing the anti-detonaw h h r tio of xy n to tri-is uty n s at tion characteristics of gasoline, which comprises least 101 f r 11101. as adding to the gasoline an oxidation product of ERNEST M- MARKS- tri-isobutylene in an amount suflicient substan- 

